1. Field of the Invention
The present invention is directed to novel cyclopropane compounds and, more specifically, to 2-vinyl- and 2-ethylcyclopropane compounds having a carboxylate moiety and a nitrile or aryl group substituted at the 1-position on the ring. The compounds of this invention are useful as chemical intermediates, pesticides and insecticides.
2. Discussion of the Prior Art
Pyrethrin and various synthetic compounds modeled thereafter, such as allethrin, are well known and while primarily recognized for their insecticidal properties are also useful for a variety of other applications. In view of the diverse physical and chemical properties possible with such products, much effort has been directed to the synthesis of other structurally related compounds, i.e., based on the cyclopropane structure.
The number of cyclopropane monocarboxylate compounds reported having only two of the ring positions substituted is limited and compounds of this type wherein a nitrile or aryl group is present at the same ring position as the carboxylate group are even more limited. Kierstead et al. (J. Chem. Soc., 1953, 1799-1803) reported the preparation of ethyl 1-cyano-2-vinylcyclopropane-1-carboxylate by the condensation of ethyl sodiocyanoacetate with 1,4-dibromobutene-2. The ability to obtain other related compounds was restricted, however, due to the limitations of the condensation reaction.
In U.S. Pat. No. 4,220,591 insecticidal cyclopropane esters are prepared via a carbene insertion reaction with a phenyl acrylic acid. The products conform to the formula ##STR1## wherein R.sub.1 is hydrogen or a methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, fluoro, chloro, bromo, methyl, ethyl, nitro or amino group, and R.sub.2 is a hydrogen or methyl group or R.sub.1 and R.sub.2 together form a methylenedioxy group; R.sub.3 L is hydrogen, or a lower alkyl group, or one of the following groups (a) to (d):
(a) m-phenoxybenzyl PA0 (b) 2-benzyl-4-furylmethyl PA0 (c) .alpha.-cyano-m-phenoxybenzyl PA0 (c) 3,4-methylenedioxy-benzyl, and PA0 2-methyl-1-pentanol PA0 2-ethylhexanol PA0 2-octanol PA0 2,6-dimethyl-4-heptanol PA0 dodecanol PA0 hexadecanol PA0 octadecanol PA0 allyl alcohol PA0 3-methyl-1-buten-3-ol PA0 3-ethyl-1-buten-3-ol PA0 3-methyl-3-penten-1-ol PA0 1,4-pentadien-3-ol PA0 5-cyclohexylidene-2-pentanol PA0 2-methyl-2-hepten-6-ol PA0 5,6-dimethyl-5-hepten-2-ol PA0 6,10-dimethylundeca-5,9-dien-2-ol PA0 3,7,11-trimethyldodeca-1,6,10-trien-3-ol PA0 cyclopentanol PA0 cyclohexanol PA0 4-methylcyclohexanol PA0 3-cyclobutyl-2-propen-1-ol PA0 3-cyclopentyl-2-propen-1-ol PA0 3-cyclohexyl-2-propen-1-ol PA0 3-cycloheptyl-2-propen-1-ol PA0 3-(4-chlorophenyl)-3-methyl-2-propen-1-ol PA0 3-(4-methylphenyl)-3-methyl-2-propen-1-ol PA0 3-(4-methylphenyl)-2-butyl-2-propen-1-ol PA0 3-(4-methoxyphenyl)-1-methyl-2-propen-1-ol PA0 3-(1-naphthyl)-2-propen-1-ol PA0 3-(4-chloronaphth-1-yl)-2-propen-1-ol PA0 3-(4-methylnaphth-1-yl)-2-propen-1-ol PA0 benzyl alcohol PA0 (3-phenoxyphenyl)carbinol PA0 (3-thiophenyl)carbinol PA0 2,4-dimethylbenzyl alcohol PA0 2,4,6-trimethylbenzyl alcohol PA0 4-allylbenzyl alcohol PA0 2,6-dimethyl-4-allylbenzyl alcohol PA0 4-(3'-methylbenzyl)benzyl alcohol PA0 4-(2',4'-dimethylbenzyl)benzyl alcohol PA0 2,6-dichlorobenzyl alcohol PA0 benzhydrol PA0 cinnamyl alcohol PA0 p-methoxycinnamyl alcohol PA0 2,4,5-trimethoxycinnamyl alcohol PA0 p-benzylcinnamyl alcohol PA0 p-benzyloxycinnamyl alcohol PA0 m-bromocinnamyl alcohol PA0 3-chloro-4-methoxycinnamyl alcohol PA0 o-methoxycinnamyl alcohol PA0 p-isopropoxycinnamyl alcohol PA0 p-phenoxycinnamyl alcohol PA0 p-methylcinnamyl alcohol PA0 p-(methylphenethyl)cinnamyl alcohol PA0 phenol PA0 cresol PA0 eugenol PA0 isoeugenol PA0 thymol PA0 .alpha.-hydroxyacetophenone PA0 cyclohexylphenol PA0 t-butylphenol PA0 nonylphenol PA0 naphthol PA0 2-phenoxyethanol PA0 diethylene glycol monomethyl ether PA0 triethylene glycol monoethyl ether PA0 monoethanol amine PA0 diethanol amine PA0 triethanol amine PA0 N-aminoethylethanol amine PA0 2-(2-aminoethoxy)ethanol PA0 3-Bis(2-hydroxyethyl)aminopropylamine PA0 N-hydroxyethylethylene diamine PA0 N-methyldiethanol amine PA0 2-(2-(3-aminopropoxy)ethoxy)ethanol PA0 2-methylaminoethanol PA0 2-dimethylaminoethanol PA0 2-diethylaminoethanol PA0 N-2-hydroxyethylacetamide PA0 2-anilinoethanol PA0 2-N-ethylanilinoethanol PA0 1-dimethylamino-2-propanol PA0 1-(2-aminoethylamino)-2-propanol PA0 4-(2'-thenyl)benzyl alcohol PA0 furfuryl alcohol PA0 (3-furyl)carbinol PA0 thiofurfuryl alcohol PA0 4-(2'furfuryl)benzyl alcohol PA0 (5-benzyl-3-furyl)carbinol PA0 2-(2',4'-dimethylbenzyl)-4-furfuryl alcohol PA0 (5-benzyl-2-furyl)carbinol PA0 (4-benzyl-5-methyl-2-furyl)carbinol PA0 2-4'-methylbenzyl)-5-furfuryl alcohol PA0 (3-methyl-2-furyl)carbinol PA0 (2-methyl-3-furyl)carbinol PA0 (5-methyl-3-furyl)carbinol PA0 (5-methyl-2-furyl)carbinol PA0 (2,5-dimethyl-3-furyl)carbinol PA0 (2,4,5-trimethyl-3-furyl)carbinol PA0 (5-allyl-2-furyl)carbinol PA0 (5-allyl-3-furyl)carbinol PA0 5-hydroxymethyl-2,2'-difurylmethane PA0 4-hydroxymethyl-2,2'-difurylmethane PA0 (4,5-benzo-2-furyl)carbinol PA0 (4,5-benzo-3-furyl)carbinol PA0 5-phenoxy-2-thienyl alcohol PA0 N-hydroxymethyl-3,4,5,6-tetrahydrophthalimide PA0 N-hydroxymethyl phthalimide PA0 N-hydroxymethyl thiophthalimide PA0 N-hydroxymethyl-3,6-dihydrophthalimide PA0 N-hydroxymethyl dimethylmaleimide PA0 N-hydroxymethyl methylethylmaleimide PA0 N-hydroxymethyl phenylmethylmaleimide PA0 3-hydroxymethyl-5-benzyl-1,2,4-oxadiazole PA0 1-benz-4-hydroxymethylpyrazole PA0 3-methyl-2-cyclopenten-4-ol-1-one PA0 2-allyl-3-methyl-2-cyclopenten-4-ol-1-one
R.sub.4 and R.sub.5 are the same or different groups and each is a fluoro, bromo, chloro or methyl group.